Manufacture of acetylene and mixtures of acetylene and hydrogen cyanide



y 5, 1954 J. L. BILLS 2,679,544

MANUFACTURE OF ACETYLENE AND MIXTURES 0F ACETYLENE AND HYDROGEN CYANIDE Filed Aug. 7, 1953 3 Sheets-Sheet 2 w m w M 53% 35 w 2 w. n z

J. BILLS' 2,679,544 MANUFACTURE OF ACETYLENEAND MIXTURES OF ACETYLENE AND HYDROGEN CYANIDE Filed Aug. 7, 1951 5 Sheets-Sheet 3 C75A/A/Z. 5/115, w

A 12%..4 0. MW

Patented May 25, 1954 MANUFACTURE 'TURES IOF 'ACETYLENE AND CYANIDE OF ACETYLENE AND MIX- HYDROGEN John :L. Bills, Long Beach, Calif., assignor to Union Oil Company of California, Los Angcles,

Calif., a corporation of California Application August 7, 1951, Serial No. 240,728 21 Claims. (01. 260679) -1 This invention relates'to themanuiacture of acetylene, and in particular concernssan improved process forobtaining acetylene 'by the :partial oxidation of hydrocarbons. Italso relates to a process whereby a mixture: of hydrogen cyanide and acetylene is producedin a singleoperation carried out under conditions of high temperature and short reaction time.

It is known that'acetylene maybe obtained by the partial oxidation of hydrocarbons particularly saturated aliphatic. hydrocarbons such as methane, ethane, propane, natural gas,etc., with oxygen or an oxygen-containin gas such asair. Such oxidation, however, does not occur to any significant extent except at .elevated temperatures which favor a varietyof sidereactions, and consequently the yields of acetylene realized have been far below theoretical. I When airis employed as the oxidizing agent the yield of acetylene-is such conditions the yield of acetylene has not amounted to more than about 40 per cent, based on the amount of'hydrocarbon consumed in the reaction. Such low yieldand the highcost of the pure oxygen required, particularly the latter,

have rendered the process commercially imprachydrocarbons, particularly normally gaseous satagent.

A further object is'to 'providea satisfactory method for the simultaneous production of hydrogen cyanide and acetylene.

A still further objectis to provide a satisfactory method forproducing. a mixture of hydrogen cyanide and acetylene by reactionbetween certain hydrocarbons, oxygen andammonia.

.Other objects will be apparent-fromthefollowemployment of the .for' from about 0.001 to about 0.05

ing detailed description of the invention, and various advantages not specifically referred to herein will occur to those skilled in the art upon invention in practice.

I have now found that the above and related objects may be realized in a process based on the discovery that a highly exothermic reaction between hydrocarbons and oxygen to form acetylene may be induced by'admixing hydrogen with a suitably preheated reactant gas mixture comprising the hydrocarbon and oxygen, and that by limiting the period of time over which such'reaction is allowed to take place, the acetylene product may be obtained in relatively high-yield. More particularly, I have found that when hydrogen is admixed with a preheated reactant gas mixture essentially comprising a hydrocarbon and oxygen, a reaction occurs accompaniedby a very rapid increase in the temperature of the mixture. The temperature ultimately attained in the mixture is herein referred to as the reaction temperature, and varies directly with the temperature vof the reactant gas at the time it is admixed with the hydrogen. The latter temperature is herein referred to as the -preheat temperature. Accordingly, the reaction temperature may be controlled-by varying the preheat temperature. By so controlling the reaction temperature to values between about 1100 C. and about 1500 C., and by limiting the period of time over which the gas mixture is permitted to rethereafter immediately cooling the gas mixture to a temperature at which substantially no further reaction takes place, e. g., to about 650 'C. or lower, acetylene may be obtained in yields of 50 based on the amount of hydrocarbon consumed. I have also found that the admixed with the preheated reactant gas mixture comprising a hydrocarbon and oxygen may advantageously be employed in admixture with certain other gases.

The invention thus consists in the process for the production of C. and about to take place second; and the product said mixing is between about 1100 1500 C. (2) allowing such reaction (3) thereafter immediately cooling gas to a temperature at which substantially no further reaction occurs. When it is desired to produce the acetylene in admixture with hydrogen cyanide, ammonia is included in the reactant gas as is hereinafter more fully explained. Such process is conveniently carried out by passing the reactant gas comprising the hydrocarbon and oxygen through a preheating zone and thence into a reaction zone wherein the preheated reactant gas is admixed with hydrogen and wherein the aforesaid reaction occurs, the temperature attained by the reactant gas in the preheating zone, i. e., the preheat temperature, being such that a reaction temperature of betweenabout 1100 C. and about 'l500 C. is attained in the reaction zone upon the admixing of the hydrogen with the preheated reactant gas, and withdrawing the resulting product gas from the reaction zone and. cooling it to a temperature at which substantially no further reaction occurs within from about 0.001 and about 0.05 second after the admixture of the hydrogen with the preheated reactant gas. By employing such procedure, acetylene may be produced from hydrocarbons and air in yields considerably higher than those realized in previous processes which have required the use of pure oxygen. The formation of free carbon is substantially eliminated, and the amount of carbon dioxide formed by side reactions is greatly reduced. Furthermore, the reaction induced by the addition of the hydrogen to the preheated reactant gas is more highly exothermic than that involved in the previously known processes, and accordingly the heat requirements of the present process are lower. Substantially the only heat consumed is that required to preheat the reactant gas and the hydrogen. Other advantages of the present process lie in the simplicity of the equipment required and in its adaptability to the application of various economical engineering techniques.

I am aware that it has been proposed to admix hydrogen with a reactant gas mixture comprising a hydrocarbon and oxygen prior to the passage of such mixture through a high temperature reaction zone for the. production of acetylene, but I have found that the yields of acetylene realized by such procedure are considerably lower than those attained by adding hydrogen to the reactant gas mixture after the latter has been suitably preheated. Similarly, the present process differs from the proposal to produce acetylene by passing a hydrocarbon through a high temperature flame such as is produced by the combustion of hydrogen in that an entirely different type of reaction is involved, namely oxidation rather than pyrolytic cracking, and in that the hydrogen is not consumed by combustion to form a flame but may be recovered from the product gas and recycled for re-use in the process.

The nature of the invention may readily be understood by reference to the accompanying drawings which form a part of this specification. In said drawings, Figure l diagrammatically represents a longitudinal cross-section of a simple apparatus which has been employed experimentally to demonstrate the nature of the invention. Figure 2 represents a longitudinal cross-section of a somewhat different form of reactor adapted for larger-scale operation. Figure 3 illustrates the relationship that exists between the preheat temperature and the reaction temperature at various points along the length of the reaction zone, and demonstrates the fact that the reaction between the hydrocarbon and product gas exit oxygen is initiated at the point of the addition of the hydrogen. Figure 4 illustrates the same relationship as it exists when a mixture of hydrogen and nitrogen is employed instead of pure Figure 5 relates to the simultaneous production of acetylene and hydrogen cyanide according to one embodiment of the invention, and illustrates the relationship between the yields of hydrogen cyanide and acetylene and the preheat temperature.

Referring now to Figure l, the illustrated apparatus consists of a quartz tube H one end of which is constricted to form a relatively small A relatively large diameter side-arm I3 is positioned near the constricted end of tube H, and serves as an exit conduit for the product gas. A relatively small diameter side-arm I4 is positioned near the opposite end of tube H, and serves as a hydrogen inlet conduit. The open end of tube H is fitted with a stopper l5 which closes tube H and coaxially supports tube I6 which extends within tube II for a portion of its length. Side-arm I1 is positioned near the exterior end of tube l6, and serves as an inlet conduit for the reactant gas. The exterior end of tube 16 is closed by stopper 18 through which passes a platinum thermocouple lead 19. Similarly, opening l2 of tube II is closed by stopper 20 through which passes a platinum-iridium thermocouple lead 2!. Thermocouple leads l9 and 2| are joined within tube H to form thermocouple junction 22, and are connected exteriorly to pyrometer 23 which indicates the temperature of thermocouple junction 22. Thermocouple leads l9 and 2| are capable of horizontal motion through stoppers l8 and 20, respectively, and accordingly the thermocouple junction 22 may be positioned at any desired point along the axis of tubes H and I8 and the temperature at that point will be indicated by pyrometer 23. A portion of the length of tube H is surrounded by an electric heating element 24, which in turn is surrounded by insulation 25 provided to minimize heat losses to the atmosphere. The length of heating element 24 defines preheating zone A within tube I6, and within tube I I reaction zone B extends from the end of tube IE to the point where the gas mixture passing through tube II is cooled to a temperature at which no further reaction occurs. The latter is accomplished by directing a current of air from conduit 26 against the outside of tube H as shown. Reaction zone B is surrounded by insulation 21 which serves to minimize heat losses to the atmosphere, and 13 leads to conventional means, not shown, for collecting and sampling the product gas. This apparatus operates as follows: The reactant gas, consisting of a suitable mixture of a hydrocarbon and oxygen or air is introduced into tube I6 through reactant gas inlet I! as shown. As the reactant gas passes through preheating zone A within tube IE it becomes heated to the desired preheat temperature by heating element 24 which is controlled to produce such temperature in the reactant gas issuing from the open end of tube [6 within tube H. The hydrogen is introduced into tube I through hydrogen inlet [4, and likewise becomes heated to the preheat temperature as it passes through the annular space between tubes II and I6 adjacent to heating element 24. At the open end of tube l6 within tube H, i. e., at the end of the preheating zone, the hydrogen mixes with the preheated reactant gas and reaction occurs with the formation of acetylene as the gas mixture Selected Temperature, 0., at'Points AlongLengthof Tube 11,-. Inches iromand the reactant gasa and hydrogen werehintro ducedinto their respective inlets at the rates specified above.

Beginning of Preheating. Zone Yield of Experi- Preheat Acetylene 1 men; 3 6 Percent I 11 12 13 14 15 l6 l7 18 19 1 1, 120 l, 110 1, 110 1, 110 1,126 1, 202 1, 316. 1, 320 1, 253 1,100 52.0 2 1, 075 1, 066 1,066 1,070 1, 083 1, 164 1, 282 1, 290 1,236" 1, 048' 51. 2 3 l, 017 1, 017 1 030 reaction zone B may be varied by sliding tube 46 in or out of stopper I5, so that the time re- E'zvample I The apparatus was constructed substantially as shown in Figure 1, tubes H andv l6 having inside diameters of about %and about. 4; inch,

pre-selected preheat temperatures. Four experiments were carried out under the following conditions:

23.1% by vol.

76.9% by vol.

8.65 s.: c. f./hr. 4.6 s. c. f./hr.

0.008 sec.

Percent by volume Methane 89.5 Ethane 6.3 Carbon dioxide 0.8 Propane 3.4-

In each experiment theheating element was, set to provide a pre-selectecLpreheattemperature 751 l, 036 1, 104 l, 253 1, 278 1, 228 1, 057 49. 6 4 75 968 972 978 988 1,074 1, 205 l, 223 1, 178 1, 008 47. 6

1 Based on amount of natural gas consumed.-

These'data are presentedigraphically in Figure 3. It wilLbe,notedthatthexaddition of the hydrogen-to'the preheated reactant gas eifects a very rapid increase" in temperature along the length of the reaction zone, and that the maximum temperature attained. within the reaction zone varies directly Withthe preheat temperature. This increase.

the. hydrogen zone atatemperaturesomewhathigher than that which had been ore-selected. as the preheat temzone along the.

Example 11 The.- apparatus and T procedure employed Werethe same as--in Example *1. Reaction conditions were as follows:

Reactant gas:

Naturalgas 23.1% by vol. Air 76.9% by vol.

Ratev of. feed, .reactantgas- 8.65 s. c. f./hr.

Rate of feed, hydrogen 4.6 s. c. f./hr. Vol. ratio, hydrogen/reactantgas 0.53/1. Residence time within reaction 0.008.

zone. Preheat temperature 1100 C. Reaction temperature, max. 1290 C.

'I'heiproduct. gas obtained contained (water-free basis.)

Percent by'volume Acetylene 3.6 Methane 5.0 Ethylene 0.4 Carbon: monoxide 5.7 Carbon dioxide 0.5 Nitrogen 42.8 Hydrogen 42.0.

Material balances were as follows:

Per cent Natural gas converted to acetylene 3'7 .8

Natural gas converted to carbon monoxide 29.8 Natural gas converted to other products 6.2 Natural gas unconverted 26.2

Yield of acetylene, based on natural gas supplied 37.8 Yield of acetylene, based on natural gas consumed 51.2

Methane 24.6% by vol. Air '75.4% by vol. Rate of feed, reactant gas 8.15 s. c. f./hr. Rateoffeed,added gas 6.0 s. c. f./hr.

Vol. ratio, added gas/reactant gas 0.74/1. Preheat temperature 1150 C. Residence time within reaction 0.008 sec.

zone.

The procedure and apparatus employed were the same as those of the preceding examples. In the first experiment, in which hydrogen was employed as the added gas, the yield of acetylene was 44.1 per cent, based on the methane consumed. In the second experiment, in which nitrogen was substituted for the added hydrogen, the yield of acetylene was only 30.2 per cent, based on the amount of methane consumed. By way of comparison, the yield of acetylene obtained when the reactant gas was passed directly through the reactor without the addition of any gas to the reaction zone was 31.4 per cent, based on the amount of methane consumed.

Example IV In order to demonstrate the use of hydrocarbons other than methane and natural gas in the present process, five experiments were carried out employing ethylene, propane, kerosene, light petroleum naphtha, and cyclohexane, respectively, as the hydrocarbon reactant. The kerosene had a specific gravity of about 0.811 and a boiling range of 348 to 523 F. The petroleum naphtha had a specific gravity of about 0.633 and a boiling range of 83 to 100 F. The conditions under which these experiments were carried out and the results obtained are set forth in the following table:

Considering nowthe essential operating variables in somewhat greater detail, the reactant gas consists essentially of a proportioned mixture of a hydrocarbon and oxygen. A wide variety of hydrocarbons are suitable, but best results are obtained with non-aromatic hydrocarbons, particularly those which are normally gaseous or liquid and boil below about 400 C. under atmospheric pressure. The term non-aromatic hydrocarbon is herein employed as a generic term including saturated and unsaturated aliphatic and cycloaliphatic hydrocarbons but excluding aromatic or benzenoid hydrocarbons. The normally gaseous saturated aliphatic hydrocarbons, particularly methane and natural gas, are especially preferred by reason of their low cost and ease of handling. Hydrocarbon mixtures, e. g., mixed refinery gases and various petroleum distillates, are also suitable. When employing a liquid hydrocarbon reactant, exterior means are provided for vaporizing the same prior to its admixture with the oxygen and/or prior to its introduction into the preheating zone, or such vaporization is effected within the preheating zone itself. The oxygen reactant is pure oxygen itself, oxygen-enriched air, ordinary air, or any other gas containing free oxygen. As previously stated, air is preferred by reason of its lack of cost, and it is one of the features of the present process that the results obtained employing air are comparable or better than those of previous processes in which pure oxygen was employed. The mole ratio of hydrocarbon to oxygen in the reactant gas varies between rather wide limits, depending upon the identity of the hydrocarbon. When the hydrocarbon is one of relatively high molecular weight, e. g., a petroleum distillate such as kerosene, as many as 50 moles of oxygen should be provided per mole of hydrocarbon. On the other hand, when the hydrocarbon is one of low molecular weight, e. g., methane, an excess of the hydrocarbon is employed so that the mole ratio of hydrocarbon to oxygen is suitably between about 1.33/1 and about 2.0/1. Thus, the mole ratio of hydrocarbon to oxygen varies from 0.02/1 to 2.0/1 depending upon the nature of the hydrocarbon. When the oxygen reactant is provided in the form of air and the hydrocarbon is natural gas, the reactant gas may comprise from about 17 to about 30 per cent by volume of natural gas and, correspondingly, from about 83 to about per cent by volume of air. When the reactant gas comprises air and a petroleum distillate such as kerosene, it may contain from about 4 to about 10 per cent by volume of the hydrocarbon and from about 96 to of air.

The amount of hydrogen which is admixed with the reactant gas within the reaction zone may be varied considerably.

about per cent by volume Usually, however, from Experiment No Hydrocarbon Reactant Gas Hydrocar on Air Rate of Reactant Gas Feed, s. c. f.lhr.. Rate of Hydrogen Feed, 5. c. f./hr Preheat Temperature, Re action Temperature, max, Preheat Time, sec Reaction Time, sec Acetylene in Product Gas, percent by vol". Yield of Acetylene. based on hydrocarbon supplie Yield of Acetylene,

consume .ac'zac re about 0.5 to about :moles, preferably from about 1.5 to about .3 moles, of hydrogen are provided per mole of hydrocarbon in :the reactant igas. Such added hydrogen is.preferably,.:but,not necessarily, preheated prior to itsintroduction into the reaction zone. .In the reactors shown :in Figures 1 and 2 such preheatingis inherently provided by the design. of :theapparatus. However, independent means-for preheating the hydrogen may be employed if desired.

The temperature to .which'the reactantvgas is preheated prior to its introduction'into the -re action zone and admixture therein with the hydrogen is such that the temperature attained in the reaction which 18 inclucedwby:said;admix ing is between about.1100 C. and about 1500-;C., preferably between about 1275 C. .gand about 1375 C. The preheat temperature'necessary to attain a reaction temperature within this range depends upon a number of factors, including the composition of the reactantgas, and the residence time within the preheating zone. these variables are factors which contribute to the possibility of reaction. occurring between the gas prior to preheating the same, and to pass the mixture through the preheating zone at a relatively high rate of flow. However, certain engineering advantages lie inse arately preheating the components of, the reactant reaction zone. Under ordinary conditions of operation the preheat temperature will bebetween about 600 C. and about 1150 C. with a preheat time between about 0.1 and about 0.005 second. When air is employed as the source of oxygen the preheat temperature will usually-be in the upper end of this range, e.-g., from about 950 C. to about 1150 C. When pure oxygen is employed the preheat temperature will be somewhat lower; e. g., 600-1000 C.

The reaction drawn from, the reaction zone.

Various types of apparatusmaybe employed in practicing the process of the, invention. However, it has been found thatbest results are hydrogen mixture to in. a direction concurrent with the -latter, as is accomplished, in the apparatus of Figures 1;, and 2.

Such reactor-may providafor the additiongofthe the r actant gas stream Alternatively, the stream of hydrogenand inert gas may be tangentially introduced into the re- Other means of securing non-turbulent mixing of gas streams areiknown in the art. "As previously mentioned, it is also desirable that the flow of the preheated reactant gas prior toits introduction into :the reaction zone be substantially unobstructed.

Figure 2 shows a reactor which is very similar in principle to "that ofFigure 1,'but which is employed for larger-scale operations. Said reactor consists of a refractory tube 3| vertically disposed withinfurnace-BZ, :which is constructed of fire-brick or other refractorymaterial. lower end of tube 3| coincideswith an opening '33 in the floor of; furnace 32, and thus communicates with quenching chamber :34 located directly below furnace 32. The-upper endof tube 3| passes throughtheroofof furnace 32 and ter- Packing gland Hi-serves to form agas-tight con nection between rtubegsl and fitting 3'5. Fitting gas; inlet ,3 I within tube 3 l flue gas generated by the burners. ing chamber 534 located beneath furnace 32, water sprays 42a to 42d are positioned so as to direct sprays of water into the gas stream issuing from opening-33 in the furnace floor. A gas outlet 83 the upper part of cooling chamber other to the. where the 42a to 42.

point :within cooling chamber .34 hot -gases are cooled; bywater sprays the cooled gas is withand is passed to storage. from a reactant methane sprays 42a to 4211, and drawn through outlet 43 A typical product gas obtained gas comprising 25 per cent by volume of 12 Also, since the inert gas has a cooling effect within the reaction zone, the use of mixtures containing relatively large proportions of the inert gas requires the use of higher preheat temand '75 per cent by volume of air consists of: peratures in order that the necessary reaction temperature be attained in the reaction zone. Acetybne i fii fi On the other hand, the cost of separating hy- Methane drogen mixtures from the product gas increases Ethylene 0A with the concentration of the hydrogen 1n the Carbon monoxide 10 mixture. Accordingly, the optimum 0011113051- Carbon dioxide tion of the mixture of hydrogen and inert gas Nitrogen 431) will be determined by balancing the cost of sep- Hydmgen 4L6 arating the mixture from the product gas against the cost of providing the additional heat which 100 0 the inert gas requires. Usually, the optimum gas mixture will contain from about 85 to about As has beenpreviously mentioned, the hydr 95 per cent by volume of hydrogen and from gen which is introduced into the reaction zone about 5 t about 5 per t by v lume or the and therein admixed the preheated reactant inert gas The operating ariables of the process gas in accordance with the invention may be emare not materially changed by employing t ployed in admixture with certain other gases. hydrogen in admixture with an inert gas rather Any inert gas, i. e., any gas which does not react than in pure form with the ether components of the System under The following examples illustrate practice of the conditions prevailing in the reaction zone, th i v ti employing the hydrogen in admixmay be so employed in conjunction with the ture with various other gases, but are not to be drogen. However, the use of nitrogen and carconstrued as limiting the invention bon monoxide, as well as mixtures of the same, in combination with the hydrogen is particularly Example V advantageous from an engineering standpoint. As shown by t data, presented in Example 11 Four experiments were carried out as descrlbed above, the product gas for the most part comm Example I except} that the hydrogen prises hydrogen, nitrogen, and carbon monoxide dllced lnto the reactlqn Zone was lfelilaced y a in addition to unreacted hydrocarbon and the hydrogen-nitr m tu me 95 p acetylene product. While it is possible to sep- Cent by Volume of hydrogen n 5 P nt of arate all of these components in substantially nitrogen. The operating conditions were subpure form and thus recover pure hydrogen for stantially the same as in Example I except that re-use in the process, it is much more simple and slightly different preheat temperatures were emeconomical first to separate the acetylene and ployed. The data obtained are tabulated as unreacted hydrocarbon, and then to treat the follows:

Temp, 0., at Points Along Length of Tube 11, Inches from Selected Beginning of Preheating Zone Yield of Experiment Preheat Acetylene, Temp, 0 Percent 11 12 14 15 15.5 16 17 10 1 Based on amount of natural gas consumed.

'These data are presented graphically in Figure remaining gas mixture to separate a mixture of hydrogen and nitrogen, or of hydrogen and carbon monoxide, or a mixture of all three, suitable for re-use in the process as the gas which is admixed with the reactant gas in the reaction zone. Accordingly, employing the hydrogen in the form of a mixture with nitrogen or carbon monoxide or both is superior to employing the hydrogen in pure form from the standpoint of simplicity and economy in recovering the hydrogen from the product gas for re-use in the process. Also, additional advantage lies in the fact that somewhat improved yields of acetylene are obtained when the hydrogen is employed in admixture with an inert gas. Such mixture of and inert gas may comprise from as little as about 30 up to 100 per cent by volume of hydrogen and, correspondingly, from about 70 down to zero per cent by volume of the inert gas. Regardless of the composition of such mixture, however, the hydrogen should be provided in the amount hereinbefore specified, and the volume of the mixture which must be supplied to the reaction zone will thus increase with decreasing concentration of the hydrogen in such mixture. 75

hydrogen 4. It will be noted that the curves of Figure 4 are substantially the same as those of Figure 3, demonstrating that the principle of the invention is not limited to the use of the hydrogen in pure form. It will also be noted from Table 2 that the yield of acetylene increased with increasing preheat and reaction temperatures up to a certain point, after which it decreased to some extent. This is considered to be due in part to the fact that in experiment 4 the reaction temperature was somewhat above the optimum for the particular reactant gas employed. It is also due to the fact that at higher preheat temperatures reaction occurs to an appreciable extent between the natural gas and oxygen within the preheating zone in the absence of the hydrogen-nitrogen mixture. Apparently, during such reaction a substantial amount of the natural gas is converted to products other than acetylene, e. g.,carbon dioxide, which results in a lower ultimate yield of acetylene.

Example VI The effect of varying the composition of the :13 1:4 mixture oihydrogenzand inertagasupon' the yield about 145 ft./sec.,acorrespondingzto a residence of acetylene was adeterminedzby .axsetof seven time within .the :reaction zone of..eabout .0007 experiments carried out .under the following second. The yield .rofiiacetylene :obtained was conditions: 49.6 per centbased zontthernatural :gas. consumed, Reactant gas: 5 and 33.8 per cent2.based:;on;the natural gassup- Methane by VOL p dt t r t Air 75.4% by vol. .EmampleTX Inert, gas Nitrogen. Rate of feed, reactant gas "8.15 so. f./hr. 10 fi zgfg 24 67 by vol Rate of feed, hydrogen mixture 6.0 s. c; f./hr. Air .1 by V01. ratio, hydrogen'mixture/re- H T o ydrogen mixture. t gas /1- Hydrogen by V01 Preheat temperature 1150" C. Nitrogen 2 1% I Residence time in reaction.zone 0.008 sec. Carbon by vol Each experiment was carried-.outas: described in Rate of feed, reactant gas 15.64 s. c. f./hr. Example I. The data obtained-are summarized Rate of feed, hydrogen-mixture 10.52 s. c. f./hr. as follows: Preheat temperature ..1150C. Residence time in preheat.zone 0.005 second. oomposmonpofflydmgenp Residence time in reaction zone- 0.004 second. xt r yield of Volume ratio, hydrogen mixture/ Experiment Acetylene, reactant gas 0.67/1,

H2, Percent N2, Percent Percent y l. by The procedure employed was the same as in the preceding examples. The product gas contained 8g 8 2-8 (water-free basis) g 8 g 2 Acetylene 'Per cent by volur2n6e 233 2323 gjg M thane 6.9 333 456 Ethylene 0,2 Carbon monoxide 5.2- Based on amount of methane consumed. Carbon dioxide 03 It will'be noted from these data that the. use Oxygen 0.1 of hydrogen-nitrogen mixtures containing from Nitrogen 40.2 as little as 1 or less to about70 per cent by vol- Hydrogen 44.5 ume of nitrogenandfrom 99 or more to about 30 per cent by volumeof hydrogen gives acetylene 100.0 yields as good as or better than those obtained Material balances were 'asfollows: when purehydrogen is employed. Percent 40 Methane.convertedtoeacetylene 30.3 Example VII Methane converted tocarbonmonoxideflu 23.7 A set of experiments identicalwith those of Ex- Methane converted toiotherl p duct 4.7 ample VI were carried out-employing carbon M h u c rted 40.8 monoxideinsteadof nitrogen astheinert gas. Yield of acetylene, based: on methane sup- In general, the results werethe same as those p i d 30.8 observed inExample VI. 'Themaximum, yield Y d f acetylene, ba d ntm thane c nof acetylene was obtained when employing a Sumed 52.0 hydrogen-carbon monoxide mixture containing Yield of oarbonmonoxide; based onmethane about 65 percent by volume .oflhy'drogen and Supplied 23.7 about 35 per cent by volume of. carbon monoxide. Yield 51f hydrogen, ba ed ":0 methane D- 11 0 p 1e Example VIII t t th 1 t As will be apparen 0, ose skiledin he 3; gggg l g gimf zgfiggl gg a art, many variations withlrespect to the dinerp g ent operating variables, reactor design, etc., are

Reactant gas: 55 possible within the herein defined scope of the Ka gas 33% invention, and various techniques may be ap- Inert 5; plied to the practice of. the invention a large Hydrdeen 85% by vol scale- Thus, r ple, it may bedesired to Nitrogen 7 57 by i effect part of h r h ating Of thereactant gas Carbon 60 and/or hydrogen mixtures .by indirect heat ex- Preheat temperature 1150 Q change alga-Inst the t Droductgas. S1m11ar1y,

various forms ofheatersand different types of In the first experiment the reactant' gas was inu y be p y o p heati g, and the troduced into the reactor at a rate of 15.64c t r m t a u rms-adapt d t c ns.c.f./hr. and the hydrogenmixturewas intro- 5 Serve heat as much as possible- Variolls educed at a rate of 10152 s.-c.-f./hr. The rate of fractory mater als may mp oy d in its conflow of gas through the reactor was thus about struction. Likewise, the product gas may be 250 linear ft./sec., and the residence time within treated in various known ways to separate the the reactionzone-was; about. 0.004zsecond. The different constituents thereof. The acetylene may yield of acetylene obtained was 44.8 percent based be separated by adsorption on asolid adsorbent, on the amount of natural gas consumed, and by selective solvent extraction, or bya. selective 27.4 per cent based on the amount of natural chemical reaction such as adsorption in aqueous gas supplied to the reactor. In the-second exsolutions of certain metal'salts. The ,unreacted periment the ratesof feed were adjusted to sehydrocarbon may be,recovered-forreeusein the cure alinear gas velocity throughithereactor of process by. selective-adsorption,onactivatedcharunreacted or are coal employing the known Hypersorption process, which process may also be adapted simultaneously to produce a mixture of hydrogen and nitrogen or carbon monoxide suitable for re-use in the process. Also the reactant gas constituents may be obtained from various sources, and the reactant gas may be prepared in various ways. Thus, a suitable reactant gas mixture may be obtained according to the process described and claimed in my copending application, Serial No. 125,663 filed November 4:, 1949, whereby a hydrocarbon gas is contacted with barium peroxide at an elevated temperature to obtain a gas mixture comprising the hydrocarbon and oxygen, and the barium oxide produced by such treatment is subsequently contacted with air at an elevated temperature to regenerate the peroxide for re-use in the process.

As previously stated, by including ammonia as an essential component of the reactant gas the acetylene product may be obtained in admixture with hydrogen cyanide. It is known that hydrogen cyanide may be obtained by reacting ammonia and oxygen or air with a low molecular weight saturated hydrocarbon, such as methane or natural gas, at high temperatures over short periods of time. The reaction which takes place may be represented by the equation: (1 mow-1500 c.

20114 30: ZNH: 2C2H2 61120 The reaction between low molecular weight hydrocarbons, such as methane or natural gas, and oxygen or air to produce acetylene takes place under substantially the same conditions, and may be represented by the equation:

Recently it has been found that gaseous mixtures of hydrogen cyanide and acetylene undergo reaction in the presence of certain catalysts to form acrylonitrile, which finds important industrial use in the manufacture of certain types of synthetic rubber and other polymeric compositions. In view of the fact that substantially the same conditions of time and temperature are employed when producing hydrogen cyanide and acetylene according to the above Equations 1 and 2, respectively, it would appear that a mixture of hydrogen cyanide and acetylene suitable ior use directly in the production of acrylonitrile could be produced by a single reaction which may be represented by an equation which is the arithmetical sum of Equations 1 and 2:

( SCH; 302 NH: HON C2H2 fiHzO I have found, however, that when it is attempted to produce a mixture of hydrogen cyanide and acetylene by reaction according to this equation, only small quantities of the desired products are obtained and the reactants are either recovered converted to other products. Thus, when a mixture consisting of 1.07 s. c. f. of methane, 3.94 s. c. i. of air, and 0.7 s. c. f. of ammonia is subjected to a temperature of about 120G C. for about 0.026 second substantially all of the ammonia is recovered as such and a large proportion of the methane is converted to carbon monoxide. The yields of hydrogen cyanide and acetylene, based on the methane employed, are only about 5.9 and about 13.8 per cent, respectively.

I have found that highly improved yields of acetylene and hydrogen cyanide may be obtained by carrying out the reaction in the presence of added hydrogen as previously described, i. e., by preheating a reactant gas mixture comprising the hydrocarbon, oxygen or air, and ammonia, adding hydrogen or a mixture of hydrogen and an inert gas to the preheated reactant gas to induce or initiate reaction, and thereafter quenching the product gas within a very short time after its formation. With the exception of the reactant gas composition, the various operating conditions and techniques employed are identical with those set forth above.

When operating the process to produce the acetylene in admixture with hydrogen cyanide, the proportions in which the reactants are employed may be varied between rather wide limits. According to Equation 3 above, the reaction requires three moles each of methane and oxygen per mole of ammonia. However, the reactant gas mixture may be made up to contain from about to about three times the amount of ammonia required by theory. When methane or natural gas is employed as the hydrocarbon reactant, from about /6 to about 1, preferably about /2, mole of ammonia is usually provided per mole of the hydrocarbon; The proportion of oxygen provided in the reactant gas mixture may likewise be varied over a considerable range, and it is possible to exercise some control over the relative yields of hydrogen cyanide and acetylene by varying the proportion of oxygen in the feed gas. In general, the formation of hydrogen cyanide is favored at the expense of the acetylene when the proportion of oxygen provided in the feed gas is greater than that required by theory. Conversely, the yield of acetylene may be increased at the expense of the hydrogen cyanide by employing less oxygen than is required by theory. Ordinarily, however, it is desired to produce the hydrogen cyanide and acetylene in substantially equimolecular quantities, and accordingly substantially the theoretical amount of oxygen is usually employed. When methane or natural gas is employed as the hydrocarbon reactant, substantially equimolecular amounts of the hydrocarbon and oxygen are employed, al though if desired from as little as /2 to as much as 2 moles of oxygen may be employed per mole of the hydrocarbon. When the hydrocarbon reactant is one of relatively high molecular weight, e. g., a petroleum distillate such as kerosene, as many as 50 moles of oxygen may be provided per mole of hydrocarbon. When the oxygen reactant is provided in the form of air, suitable allowance should be made for the nitrogen content of the air. Thus, a suitable feed gas comprising methane or natural gas, air and ammonia may consist of from about 5 to about 65 per cent by volume of methane or natural gas, from about 65 to about per cent by volume of air, and from about 5 to about 10 per cent by volume of ammonia.

The following examples illustrate the simultaneous production of acetylene and hydrogen cyanide according to the process of the invention, but are not to be construed as limiting the same.

Example X the form of and 50.0 -nolecular equivalents of ammonia was introduced into the feed gas inlet at a ra of 735 s. c. f. h., and the hydrogen was sliced into the hydrogen inlet at a rate of c. The mole ratio of hydrogen to methane was about 3/ 1. The product gas withdrawn from the reaction zone was shockcooled, passed through a cold trap, and thence to a conventional gas sampling system. A series of six runs was made under these conditions, the length of the preheating zone (and hence the preheat temperature) being varied by sliding the feed gas inlet tube in or out of the stopper. The data obtained are tabulated as follows:

Point of Approximate Hydrogen Run Hydrogen Preheat Cyanide e N 0. Addition, Temperature, Yield, Perez? 3 Inches 1 0. Percent 2 1 C. 300 14. 0 16. 2 2 2.0 450 19. 9 l8. 2 3 4. 0 750 26. 6 25. 4 G. 0 975 32. 5 26. 2 5 8.0 1,100 31. 9 28.4 6 1!). 0 1, 200 0. 6 0. 0 wh hh Distance in inch-cs l1 in beginning of heating section. 2 Based on the cunt of ammonia employed. 3 Based 0': th ill. of methane employed.

The curves shown in Figure 5 of the accompanying drawing are plotted from the above data,

and illustrate the relationship between the yields and acetylene and the preteniperature. i. e., the temperature of the reactant gas at the time of hydrogen addition. It will be noted that in run No. 6, wherein the of hydrogen cyanide preheat temperature was so high that reaction occurred prior to introduction of the hydrogen, substantially no hydrogen cyanide or acetylene was obtained.

Exa'lnple XI The apparatus and procedure employed were the same as that described above in Example I. The operating conditions were as follows:

Feed gas:

Methane 15.4% by vol. Air 77.0% by vol. Ammonia 7.6% by vol.

Rate of feed 8.45 s. c. f./hr.

Rate of arci 65121113551511: 3.90 s. c. f./hr. Mole ratio, oxygen to methane l/ 1.

Mole ratio, hydrogen to methane 3/1.

Average reaction temperature 1200 C. Preheat temperature 950 sec. Reaction time 0.003 sec.

The composition of the product gas on a waterfree basis was as follows:

Per cent by volume The yield of hydrogen cyanide was 38.7 per cent, based on ammonia employed, and 79.6 per cent, based on the ammonia consumed. The yield of acetylene was 28.8 per cent, based on the methane employed, and 35.0 per cent, based on the 1'8 methane consumed. The net consumption of the added hydrogen was substantially zero.

Example XII The procedure and operating conditions employed were the same as in Example X1, except that the hydrogen introduced into the reaction zone was replaced by a hydrogen-nitrogen mixture containing 89 per cent by volume of hydrogen and 5 per cent by volume of nitrogen. The yield of hydrogen cyanide was about 72 per cent, based on the ammonia consumed, and the yield of acetylene was about 34. per cent, based on the methane consumed. Substantially identical results were obtained when the nitrogen in the hydrogen-containing gas was replaced with carbon monoxide or with a mixture of nitrogen and carbon monoxide.

Other modes of applying the principle of my invention may be employed instead of those explained, change being made as regards the materials and apparatus employed, provided the step or steps stated by any of the following claims, or the equivalent of such stated step or steps, be employed.

This application is a continuation-in-part of my copending applications Serial No. 173,132, filed August 7, 1950, and Serial No. 149,411 filed March 13, 1950, now abandoned.

I, therefore, particularly point out and distinctly claim as my invention:

1. The process for producing an acetylene-containing product gas which comprises (1) forming a reactant gas comprising oxygen and a nonaromatic hydrocarbon having a normal boiling point below about 400 0.; (2) preheating said reactant gas to a temperature below that at which reaction between the components thereof takes place to any substantial extent; (3) initiating an acetylene-producing reaction by introducing into the preheated reactant gas a hydrogeneontaining gas comprising from about 30 to per cent by volume of molecular hydrogen substantially free from atomic hydrogen and from about 70 to zero per cent by volume of a diluent gas which is inert under the conditions of said acetylene-producing reaction, the amount of said hydrogen-containing gas being sufiicient to provide between about 0.5 and about 5 moles of hydrogen per mole of hydrocarbon in the reactant gas; (4) controlling the temperature of said preheated reactant gas and said hydrogen-containing gas so that the temperature attained in said acetylene-producing reaction is between about 1100 C. and about 1500 C.; and (5) within from about 0.001 to about 6.05 second after introduction of the said hydrogen-containing gas into the said preheated reactant gas, cooling the product gas to a temperature at which substantially no further reaction occurs.

2. The process for producing acetylene which comprises 1) forming a reactant gas consisting. essentially of oxygen and a non-aromatic hydrocarbon having a normal boiling point below about 400 0.; (2) preheating said reactant gas to a temperature below that at which tween the components thereof takes place to any substantial extent; (3) initiating an acetyleneproducing reaction by introducing into the preheated reactant gas a hydrogen-containing gas comprising from about 30 to 100 per cent by volume of molecular hydrogen substantially free from atomic hydrogen per cent by volume of a diluent gas whichisinert under the conditions of said acetylene producing and from about 70 to zero reaction, the amount of said hydrogen-containing gas being sufficient to provide between about 0.5 and about moles of hydrogen per mole of hydrocarbon in the reactant gas; (4) controlling the temperature of said preheated reactant gas and said hydrogen-containing gas so that the temperature attained in said acetylene-producing reaction is between about 1100 C. and about 1500 C.; and (5) within from about 0.001 to about 0.05 second after introduction of the said hydrogen-containing gas into said preheated re actant gas, cooling the product gas to a temperature at which substantially no further reaction occurs.

3. The process of claim 2 wherein the hydrocarbon component of the reactant gas is a normally gaseous saturated aliphatic hydrocarbon.

4. The process of claim 2 wherein the hydrocarbon reactant is selected from the class consisting of methane and natural gas.

5. The process of claim 2 wherein the reactant gas comprises between about 1'7 and about 30 per cent by volume of a hydrocarbon selected from the class consisting of methane and natural gas and between about 83 of air.

6. The process of claim 2 wherein the diluent gas is selected from the class consisting of nitrogen, carbon monoxide and mixtures of carbon monoxide and nitrogen.

I. The process for producing acetylene which comprises (1) forming a reactant gas essentially comprising oxygen and a normally gaseous saturated aliphatic hydrocarbon; passing said reactant zone wherein it is heated to low that at which reaction between the components thereof takes place to any substantial extent; (3) passing a hydrogen-containing gas comprising from about 30 to 100 per cent by volume of molecular hydrogen and from about '70 to zero per cent by volume of a diluent gas which is inert under the conditions of the subsequent acetylene-producing reaction through a second preheating zone wherein said hydrogencontaining gas is preheated to a temperature below that at which any substantial amount of atomic hydrogen (4) initiating an acetylene-producing reaction by simultaneously introducing the preheated hydrogen-containing gas and the preheated reactant gas into a reaction zone, the amount of the hydrogen-containing gas so introduced being sufiicient to provide between about 0.5 and about 5 moles of hydrogen per mole of hydrocarbon in the reactant gas which is introduced into said zone; (5) controlling the preheat temperatures so that the temperature attained in said acetylene-producing reaction is between about 1100 C. and about 1500 C.; and (6) within from about 0.001 to about 0.05 second after introduction of the preheated hydrogen-containing gas and the preheated reactant gas into said reaction zone, withdrawing the product gas from the reaction zone and cooling it to a temperature at which substantially no further reaction occurs.

8. The process of claim '7 wherein the hydrocarbon reactant is selected from the class consisting of methane and natural gas.

a temperature be- 9. The process of claim '7 wherein the reactant gas comprises between about 17 and about 30 per cent by volume of a hydrocarbon selected from the class consisting of methane and natural gas and between about 83 and about '70 per cent by volume of air.

and about 70 per cent by volume gas through a first preheating :si.

10. The process of claim 7 wherein the hydrogen-containing gas and the reactant gas are preheated to a temperature between about 600 C. and about 1150 C. prior to their introduction into the reaction zone.

11. The process of claim '7 wherein the diluent gas is selected from the class consisting of nitrogen, carbon monoxide and mixtures of nitrogen and carbon monoxide.

12. The process of claim "I wherein the hydrogen-containing gas comprises between about 85 by volume of molecular hydrogen and between about 15 and about 5 per cent by volume of diluent gas selected from the class consisting of nitrogen, carbon monoxide and mixtures of nitrogen and carbon monoxide.

13. The process of claim 7 wherein the amount of the hydrogen-containing gas introduced into the reaction zone is sufficient to provide between about 1.5 and about 3 moles of hydrogen per mole of hydrocarbon reactant.

14. The process for producing acetylene which comprises (1) forming a reactant gas comprising between about 1'7 and about per cent by volume of natural gas and between about 83 and about per cent by volume of air; (2) passing said reactant gas through a first preheating zone wherein said gas is heated to a temperature between about 950 C. and about 1150 C.; (3) passing a hydrogen-containing gas comprising between about 85 and about per of hydrogen and between about 15 and about 5 per cent by volume of an inert gas selected from the class consisting of nitrogen, carbon monoxide and mixtures thereof through a second preheating zone maintained at substantially the same temperature as said first preheating zone; (4) initiating an acetylene-producing reaction within a reaction zone by simultaneously passing into said reaction zone preheated reactant gas from said first preheating zone and preheated hydrogen-containing gas from said second preheating zone, the amount of preheated hydrogemcontaining gas being sufficient to provide within the reaction zone between about 1.5 and about 3 moles of hydrogen per mole of hydrocarbon; and (5) within from about 0.002 to about 0.02 second after the introduction of the preheated reactant gas and the preheated hydrogen-containing gas into the reaction zone, withdrawing an acetylene-containing product gas from the reaction zone and cooling it to a temperature below about 650 C.

15. The process for producing hydrogen cyanide and acetylene which comprises (1) forming a reactant gas essentially comprising a non-aromatic hydrocarbon having a normal boiling point below about 400 C., oxygen and ammonia, said reactant gas containing from about to about 3 times the amount of ammonia and from about to about 2 times the amount of oxygen theoretically required for the formation of hydrogen cyahide and acetylene; (2) passing said reactant gas through a first preheating zone; (3) passing a hydrogen-containing gas comprising between about 30 and per cent by volume of molecular hydrogen and between about '10 and zero per cent by volume of a diluent gas which is inert under the condition of the subsequent acetyleneand hydrogen cyanide-producing reaction through a second preheating zone wherein the hydrogen-containing gas is preheated to a temperature below that at which any substantial amount of atomic hydrogen is formed; (4) initiating an acetyleneand hydrogen cyanide-producing reaction by simulhydrogen per mole of hydrocarbon in the reactant gas which is introduced into said zone; controlling the preheat temperatures so that the temperature attained in said acetyleneand hydrogen cyanide-producing reaction is between about 1100 C. and about 1500 0.; and (5) within 0.001 to about 0.05 second after inhydrogen-containther reaction occurs.

16. The process of claim 15 wherein the hydrocarbon reactant is selected from the class consisting of methane and natural gas.

17. The process of claim actant gas, from about 65 to about 85 per cent by volume of air, and from about 5 to about per cent by volume of ammonia.

18. The process of claim wherein the hydrothe class consisting of nitrogen, carbon monoxide and mixtures of nitrogen and carbon monoxide.

19. The process of claim 15 wherein the reactant gas and the hydrogen-containing gas are preheated to a temperature between about 600 C. and about 1150 C. prior to their introduction into the reaction zone.

20. The process of claim 15 wherein the amount of hydrogen-containing gas introduced into the reaction zone is sufiicient to provide between about 1.5 and about 3 moles of hydrogen per mole of hydrocarbon reactant.

21. A process for producing hydrogen cyanide and acetylene which comprises (1) forming a refor the formation of hydrogen cyanide and acetylene; (2) preheating said reactant gas to a temperature between about 950 C. and about 1150 C.; (3) preheating a hycarbon monoxide to a temperature between about 950 C. and about 1150 C.; (4) initiating an acetyleneand hydrogen cyanide-producing reaction by simultaneously introd g References Cited in the file of thi patent UNITED STATES PATENTS Number Name Date 2,167,471 Auerbach July 25, 1939 2,370,849 Dutcher Mar. 6, 1945 2,549,240 Robinson Apr. 17, 1951 FOREIGN PATENTS Number Country Date 332,731 Great Britain July 31, 1930 479,438 Great Britain Feb. 4, 1938 

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